Hardened artificial materials and process of preparing them



Patented Dec. 27, 1932 UNITED STATES PATENT OFFICE ARTHUR VOSS, OF FRANKFORT-ON-THE-MAIN-HOCHST, GERMANY, ASSIGNOR TO I. G.

FARIBENINDUSTRIE AKTIENGESELLSCHAFT, OF FRANKFORT-ON-THE-MAIN, GER- MANY HARDENED ARTIFICIAL MATERIALS AND PROCESS OF PREPARING THEM No Drawing. original application filed January 7,

29, 1927. Divided and this application filed April 27, 1931.

My present invention relates to hardened artificial materials and process of preparing them, more particularly to materials con- I sisting of or containing insoluble and infusible resins containing chemically entirely indifferent carboxyl groups.

The afore-said resins containing carboxylic acid groups (hereinafter referred to for convenience as resin-carboxylic acids) may be obtained by reaction between a phenolaldehyde resin and a halogen fatty acid or a salt thereof, or by reaction between a phenoxyfatty acid and formaldehyde or a substance yielding formaldehyde. I have moreover found that insoluble and infusible resins are obtained by transforming the said resins containing carboxyl groups in water-soluble compounds by neutralizing them wholly or partlally with ammonia or the derivatives thereof, as, for instance, methylamine or with the aqueous solution, pressing into a suitable mould and hardening by heating. By impregnating wood-paste which is obtainable cheaply in commerce, with the solution, it is thus possible to manufacture molded articles of any shape, such as pipes, boxes, containers, dishes, casks, barrels,-and other various kinds of? articles of general utility. Artificial m'afs ses may also be made by impregnating paper web, superposing a number of layers of thegimpregnating web, and subsequent ly hardening-the mass.

The molded articles thus obtained have 'valuable'p"perties; in particular, they are entirely Wat proof and extraordinarily resistant to mechanical and chemical action.

I According to the purpose for which the prodnets are intended there may be used instead,

of arpaper-pulp web' another filling material,-such:-as. asbestos fibers, sawdust, in-

0 faerial earth,.;powdered horn or the like.

1930, Serial No. 419,191, and in Germany September Serial NO. 533,357;

The products have a low electrical conductivity, and are, therefore, well suited for electrical insulation. They are also applicable as substitutes for shellac and the manufacture of stifi'enings for hats or caps.

By a further feature of the invention, the resin-carboxylic acids may be converted into useful hardened products by heating their ammonium salts, or salts of ammonia derivatives at a temperature above 100 C. in the presence of a polyhydric alcohol of low volatility, such as glycol, glycerin, mannitol, polyvinyl alcohol, a carbohydrate soluble in water, or the like. The hardening operation may also in this case be conducted in presence or absence of a filling material. In this method of operating, it is even possible to dispense with the conversion of the resincarboxylic acid into its salt, and the invention accordingly includes a manufacture of hardened artificial material by heating a resin-carboxylic acid at a temperature at above 100 C. in the presence of a polyhydric alcohol of low volatility, with or without addition of a filling material, for example, the resin-carboxylic acid is dissolved in alcohol, the solution is mixed with a quantity of glycerin, equimolecular to that of the resin acid, or an equimclecular quantity of another polyhydric alcohol of low volatility, such as penta-erythritol, the solution is evaporated and the residue hardened as already described. In some cases, the solvent may be dispensed with, it being suliicient merely to mix the resin-carboxlylic acid and the polyhydric alcohol, and to heat the mixture to the necessary temperature.

Products of particularly good elasticity are obtained by using as the polyhydric alcohol, polyvinyl alcohol, obtainable by saponification of polyvinyl acetate.

The following examples illustrate the invention, the parts being by weight:

(1) The resin-like product obtained; by condensation of equal parts of commercial tricresol and formaldehyde of 30.. per cent strength in the presence of about 10 per cent of an alkali is mixed, without being freed from the alkali used for the condensation,

with a quantity'of a concentrated aqueous 100 solution of an alkali such that the total quantity of the alkali present is equivalent to the quantity of the cresol used. Into the clear I aqueous solution thus obtained there is in- 5 troduced in the form of a concentrated aqueous solution, a quantity of sodium chloracetate also equivalent to the cresol used, at a temperature of about C. to C To a condensation product obtained .from 108 parts 'of cresol, 108 parts of formaldehyde of 30 per cent. strength and 30 parts of concentrated caustic soda solution of 42 B., there are added to a moderate temperature (40 C. to 50 C.) a further parts of caustic soda solution andv 116.5 parts of sodium chloraoetate, the whole being maintained at about 40 C. to 50 C. until all sodium chloracetate has been introduced, after which it is heated for a short time at C. to C. for the purpose of accelerating the reaction. The resin-acid product is precipitated by acidification with hydrochloric acid; it is a whitish resinous mass which when cold easily crumbles, but becomes soft at a moderately raised temperature. It is washed, dissolved in 400 parts of warm aqueous ammonia of 10 per cent. strength, and the clear, feebly colored solution produced which has a slightly ammoniacal smell, is mixed with an aqueous solution of 25 parts of polyvinyl alcohol. After evaporating the solution thus obtained on a water bath, there remains a clear resinous residue, which when further heated to about 150 C. to 170 C. gradually becomes convertcd into a hard mass which is entirely insoluble and infusible, but nevertheless very elastic; it may conveniently be used for the preparation of articles which are required to be resistant toward thrust or other mechanical action.

(2) 100parts of the phenol-formaldehyde condensation product known as bakelite A are caused to react in the manner already described with chloracetic acid, and the resin acid thus obtained is dissolved in aqueous ammonia as described in Example (1) The aqueous solution is mixed with 15 parts of glycerin of 97 per cent. strength, the mixture is kneaded with a quantity of paper-pulp of 22 per cent. strength, such that a uniform pasty mass is produced. The mass is freedfrom a part of the solution by pressing, the solid cake thus obtained is pressed in suitable moulds which are then heated internally or externally. There are thus obtained homogeneous hardened objects which are very resistant to mechanical and chemical actions and are distinguished by their low specific gravity.

0 This application is a division of my copendmg application Serial No. 419,191, filed January 7th,1930.

I claim:

1. The process which comprises treating henolaldehyde condensation products containing carboxyl groups with a nitrogen base selected from the group consisting of ammonia, aliphatic amines and cyclic amines and heating the water-soluble compounds thus obtained with a polyhydric alcohol to a temperature of between 100 C. and 200 C.

2. The process which comprises treating condensation products obtained from a. phenolaldehyde resin and a halogen fatty acid with a nitrogen base selected from the group consisting of ammonia, aliphatic amines andcyclic amines and heating the water-soluble compounds thus obtained with a polyhydric alcohol to a temperature of between 100 C. and 200 C.

3. The process which comprises treating condensation products obtained fromthe condensation product of phenol and formaldehyde and chloracetic acid with a nitrogen base selected from the group consisting of ammonia, aliphatic amines and cyclic amines and heating the water-soluble compounds thus obtained with a polyhydric alcohol to a temperature of between 100 C. and 200 C.

4. The process which comprises treating condensation products obtained from the condensation product of phenol and formaldehyde and chloracetic acid with a nitrogen base selected from the group consisting of ammonia, aliphatic amines and cyclic amines and heating the water-soluble compounds thus obtained with glycerin to a temperature of between 100 C. and 200 C.

5. The process which comprises treating phenolaldehyde condensation products contalmng carboxyl groups with ammonia and heating the water-soluble compounds thus obtained with a polyhydric alcohol to a tem perature of between 100 C. and 200 G.

6. The process which comprises treating condensation products obtained from the condensation product of phenol and formaldehyde and chloracetic acid with ammonia and heating the water-soluble compounds thus obtained with glycerin to a tempera.- ture of between 100 C. and 200 C.

7 As new products, insoluble and infusible resins containing chemically entirely indifferent carboxyl groups, substantially identical with resins obtainable by treating phenolaldehyde condensation products contaming carboxyl groups with a nitrogen base selected from the group consisting of ammonia, aliphatic amines and cyclic amines and heating the water-soluble compounds thus obtained with a 'polyhydric alcohol to a temperature of between100 C. and 200 C.

8. As new products, insoluble and infusible resins containing chemically entirely indifferent carboxyl groups, substantially identical with resins obtainable by treating condensation products obtained from a phenolaldehyde resin and a halogen fatty acid with a nitrogen base selected from the group consisting of ammonia, aliphatic amines and cyclic amines and heating the water-soluble compounds thus obtained with a polyhydric alcohol to a temperature of between 100 C. and 200 C. 9. As new products, insoluble and infusible resins containing chemically entirely indifferent carboxyl groups, substantially identical with resins obtainable by treating condensation products obtained from the condensation product of phenol and formaldehyde and chloracetic acid with a nitrogen base selected from the group consisting of ammonia, aliphatic amines and cyclic amines and heating the water-soluble compounds thus obtained with a polyhydric alcohol to a temperature of between 100 C. and 200 C.

10. As new products, insoluble and infusible resins containing chemically entirely indifferent carbox'yl roups, substantially identical with resins 0%tainable by treating condensation products obtained from the condensation product of phenol and formaldehyde and chloracetic acid with a nitrogen base selected from the group, consisting of ammonia, aliphatic amines and'cyclic amines and heating the water-soluble compounds thus obtained with glycerin to a temperature of between 100 C. and 200 C.

11. As new products, insoluble and infusi ble resins containing chemically entirely indifferent carboxyl groups, substantially identical with resins obtainable by treating phenolaldehyde condensation products containing carboxyl groups with ammonia and heating the water-soluble compounds thus obtained with a polyhydric alcohol to a temperature of between 100 C. and 200 C.

12. As new products, insoluble and infusible resins containing chemically entirely indifi'erent carboxyl groups, substantially identical with resins obtainable by treating condensation products obtained from the condensation product of phenol and formaldehyde and chloracetic acid with ammonia and heating the water-soluble compounds thus obtained with glycerin to a temperature of between 100 C. and200 C.

In testimony whereof, I aflix my si nature. ARTHUR OSS. 

